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. 2022 Feb 2;144(4):1729-1738.
doi: 10.1021/jacs.1c11207. Epub 2022 Jan 24.

Pickering Interfacial Catalysis for Aerobic Alcohol Oxidation in Oil Foams

Shi Zhang  1   2 , Dmytro Dedovets  2 , Andong Feng  1   2 , Kang Wang  3 , Marc Pera-Titus  1   3
Affiliations

Pickering Interfacial Catalysis for Aerobic Alcohol Oxidation in Oil Foams

Shi Zhang et al. J Am Chem Soc. .

Abstract

Oil foams stabilized by surface-active catalytic particles bearing fluorinated chains and Pd nanoparticles allowed fast and efficient aerobic oxidation of a variety of aromatic and aliphatic alcohols compared to bulk catalytic systems at ambient O2 pressure. High foam stability was achieved at low particle concentration (<1 wt %) provided that the contact angle locates in the range 41°-73°. The catalytic performance was strongly affected by the foaming properties, with 7-10 times activity increase in pure O2 compared to nonfoam systems. Intermediate foam stability was required to achieve good catalytic activity, combining large interfacial area and high gas exchange rate. Particles were conveniently recycled with high foamability and catalytic efficiency maintained for at least seven consecutive runs.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(a) FT-IR spectra of the different particles. (b) 29Si NMR MAS spectra of Pd@SiNP_F17(1–4). (c) HR-TEM micrograph of Pd@SiNP_C8(1–4). (d–f) HR-TEM/EDS micrographs of Pd@SiNP_F17(1–4).
Figure 2
Figure 2
(a) Optical images of the BnOH/xylene (1:1 v/v) system stabilized by 1 wt % Pd@SiNP_F17(1–4) as a function of stirring rate at 80 °C and 1 h. (b) Aerobic oxidation of BnOH over Pd@SiNP_C8(1–4) and Pd@SiNP_F17(1–4). Reaction conditions: 0.9 mL of BnOH, 0.9 mL of xylene, 1 bar of air, 1 wt % particles, 1500 rpm, 80 °C, 1 h. (c) Zoom-in optical image of BnOH/xylene (1:1 v/v) system stabilized by 1 wt % Pd@SiNP_F17(1–4) at 1500 rpm, 80 °C, 1 h. (d) Microscopic image of BnOH/xylene (1:1 v/v) system stabilized by 1 wt % Pd@SiNP_F17(1–4) at 1500 rpm, 80 °C, 1 h.
Figure 3
Figure 3
(a) BnAH yield and TON as a function of the particle concentration for the aerobic oxidation of BnOH over Pd@SiNP_C8(1–4) and Pd@SiNP_F17(1–4). Reaction conditions: 0.9 mL of BnOH, 0.9 mL of xylene, 1 bar air, 1500 rpm, 80 °C, 1 h. (b) Schematic representation of catalysis in particle-stabilized nonaqueous foam system in air. (c) Average bubble size and foam height at variable Pd@SiNP_F17(1–4) particle concentration at 80 °C. (d) Time evolution of the foam height for foam produced with Pd@SiNP_F17(1–4) at 80 °C.
Figure 4
Figure 4
Top: aerobic oxidation of BnOH catalyzed by a mixture of catalytic and noncatalytic particles. Bottom: schematic representation and optical images of reaction system after 1 h reaction. Reaction conditions: 0.9 mL of BnOH, 0.9 mL of xylene, 1 bar of air, 1500 rpm, 80 °C, 1 h.
Figure 5
Figure 5
(a) Interfacial contact angle and foam height as a function of the BnOH concentration over Pd@SiNP_C8(1–4), Pd@SiNP_F17(1–4), Pd@SiNP_F17(1–8), and Pd@SiNP_F17(1–16) particles. (b) BnAH yield and TON after 1 h in the aerobic oxidation of BnOH over Pd@SiNP_C8(1–4), Pd@SiNP_F17(1–4), Pd@SiNP_F17(1–8), and Pd@SiNP_F17(1–16) particles in BnOH/xylene mixtures at variable BnOH/xylene volume ratios. Reaction conditions: 1.8 mL total liquid volume, 1 wt % particles, 1 bar air, 1500 rpm, 80 °C, 1 h.
Figure 6
Figure 6
(a) Kinetic profiles for the aerobic oxidation of BnOH over (a) Pd@SiNP_F17(1–4) and (b) Pd@SiNP_F17(1–8). Reaction conditions: 0.9 mL of BnOH, 0.9 mL of xylene, 1 wt % particle, 1 bar air, 1500 rpm, 80 °C.
Figure 7
Figure 7
Recyclability and reuse of Pd@SiNP_F17(1–4) for the aerobic oxidation of BnOH over seven consecutive cycles. Reaction conditions: 0.9 mL of BnOH, 0.9 mL of xylene, 1 wt % particle, 1 bar air, 1500 rpm, 80 °C, 1 h.
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